Dinitramines



United States Patent 3,000,955 DINITRAMINES Milton B. Frankel, Pasadena, Calif., aslgnor to Aerojetgfineral Corporation, Azusa, Califi, a corporation of No Drawing. Filed June 13, 1957, Ser. No. 666,275 17 Claims. (Cl. 260-583) This invention relates to new compositions of matter and to the preparation thereof. More particularly, the invention relates to dinitramines of the following general formula:

IIIOa If. No, I? l' os R-CHrN-A-CHI-N-CHl-(iJ-CHa-N-C HrA-N-CHr R wherein R is a hydrogen, alkyl or nitroalkyl radical and A is an alkylene radical.

The dinitramines of this invention react with formaldehyde to produce nitro-substituted 1,3-diazines, as more fully disclosed in my copending US. patent application, Serial No. 666,272, filed concurrently with the present application. The nitro-substituted 1,3-diazines thus prepared are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the Warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an irnpactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The novel dinitramine compounds of this invention are prepared by condensing nitraza amines with 2,2-dinitro- 1,3-propanedio1 in accordance with the general reaction scheme set forth below:

wherein R and A are as previously defined.

To more clearly illustrate my invention, the following example is presented. It should be understood that this example is presented merely as a means of illustration and is not intended to limit the scope of the invention in any way.

Example I.--Preparation of 2,5,9,12-tetraaza-2,7,7,12-

tetranitrotridecane To a mixture of 46.5 g. (0.3 mole) of 3-nitraza-I-butyl ammonium chloride, 24.9 g. (0.15 mole) of 2,2-dinitro- 1,3-propanediol, and 100 ml. of water was added 75 m1. of water containing 24.6 g. (0.3 mole) of sodium acetate in solution. A yellow solid precipitated which was washed with water and dried to yield 34.6 g. (62.7%) of 2,5,9,l2-tetraaza-2,7,7,l2-tetranitrotridecane as a final product having a MP. of ll0-1l5" C.

Optimum results are obtained from the condensation reaction of this invention when it is conducted at a pH Patented Sept. 19, 1961 below about 8 and preferably within the range from about 4 to about 8.

Reaction temperature is not critical in the practice of this invention, the only efiect of temperature variation being a corresponding increase or decrease in reaction rate.

As a matter of convenience, the free nitraza amine starting materials of this invention are preferably generated in situ from their corresponding strong mineral acid salts by neutralizing said strong mineral acid salts with inorganic basic salts, as for example, hydroxides or carbonates, or weak organic acid salts, of alkali or alkaline earth metals. For reasons of convenience and economy I prefer to use sodium hydroxide as my free nitraza amine generating agent but other suitable agents such as calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium acetate, etc., can be used for this purpose if desired.

Any of the strong mineral acid salts such as nitric acid, hydrochloric acid, etc., salts of my nitraza amine starting materials can be used in the practice of my invention.

Nitraza amine salts useful in the practice of this invention are prepared by reacting corresponding nitraza isocyanates such as, 3-nitraza-l-butyl isocyanate, with aqueous strong mineral acid solutions, as more fully disclosed in my copending US. patent application Serial No. 666,273, filed concurrently with the present application.

It should be pointed out that mixtures of nitraza amines can be employed in the preparation of the dinitramines of this invention. It is thus within the scope of the invention to condense such mixtures of nitraza amines with 2,2 dinitro-l,3-propanediol and obtain mixtures of dinitrarnines of the general formula:

wherein the two Rs and/or the two As are the same and are respectively different. For example, the two Rs can be different alkyl or nitroalkyl radicals, respectively, or they can represent any combination of the three possible types of radical Within the scope of my invention, for example, one can be alkyl and the other nitroalkyl; one hydrogen and the other alkyl, etc. Such mixtures can be separated by conventional fractionation techniques. For reasons of convenience and economy, I prefer to employ relatively pure nitraza amines, rather than mixtures thereof, in the practice of my invention, in which case symmetrical dinitramines having identical Rs and identical A's are produced.

It will be appreciated that a wide variety of dinitrarnine compounds can be prepared in accordance with the method of my invention. For example, 4-nitraza-l-hexylamine and 3-aza-3,5,5-trinitro-l-hexylamine react with 2,2-dinitro-1,3-propanediol to yield 3,7,11,15-tetraaza- 3.93.15 tetranitroheptadecane and 2,2,4,9,9,14,l6,16- octanitro 4,7,11,14 tetraazaheptadecane, respectively. Mixtures of these two nitraza amines react with 2,2-dinitro-l,3-propanediol to produce the unsymmetrical dinitramine: 2,2,4,9,9,15-hexanitro-4,7,1 1,15-tetraazaheptadecane. Other members of this new series of compounds are prepared simply by reacting appropriate starting materials as taught herein.

I claim:

1. As a composition of matter, a dinitramine having the formula:

wherein R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals, and A is a lower alkylene radical.

2. As a composition of matter, a dinitramine having wherein R is a lower alkyl radical and A is a lower alkylene radical.

3. As a composition of matter, a dinitrarnine having the formula:

5. As a composition of matter, 3,7,l1,15-tetraaza-3,9, 9,IS-tetranitroheptadecane having the structural formula:

6. As a composition of matter 2,2,4,9,9,14,l6,16-octanitro-4,7,ll,l4-tetraazaheptadecane having the structural formula:

7. As a composition of matter, 2,2,4,9,9,15-hexanitro- 4,7,11,15-tetraazaheptadecane having the structural formula:

8. The method of preparing dinitramines having the formula:

which comprises condensing a nitraza amine having the formula:

4 with 2,2-dinitro-1,3propanediol; wherein R is a radical selected from the group consisting of hydrogen, lower alkyl and lower nitroalkyl radicals, and A is a lower alkylene radical.

9. The method of claim 8 in which the nitraza amine is generated in situ.

10. The method of claim 8 in which the nitraza amine is generated in situ from a strong mineral acid salt thereof by neutralizing said salt with an aqueous solution of a salt selected from the group consisting of the inorganic basic salts and the weak organic acid salts of the alkali and alkaline earth metals.

11. The method of preparing dinitramines having the formula:

which comprises condensing a nitraza amine having the formula:

r R-N-AC mNII,

with 2,2 dinitro-L3-propanediol; wherein R is a lower alkyl radical and A is a lower alkylene radical.

12. The method of preparing dinitramines having the formula:

which comprises condensing a nitraza amine having the formula:

with 2,2-dinitro-1,3-propanediol; wherein R is a lower nitroalkyl radical and A is a lower alkylene radical.

13. The method of preparing 2,5,9,l2-tetraaza-2,7,7, IZ-tetranitrotridecane which comprises condensing 3- nitraza-l-butylamine with 2,2-dinitro-1,3-propanediol.

14. The method of preparing 3,7,ll,l5-tetraaza-3,9,9, IS-tetranitroheptadecane which comprises condensing 4- nitraza-l-hexylamine with 2,2-dinitro-1,3-propanediol.

15. The method of preparing 2,2,4,9,9,14,l6,l6-octanitro-4,7,11,14-tetraazaheptadecane which comprises condensing 3-aza-3,S,5-trinitro-l-hexylarnine with 2,2-dinitro- 1 ,3-propanediol.

16. The method of claim 13 in which the 3-nitraza-lbutylamine is generated in situ from 3-nitraza-1-hutyl ammonium chloride.

17. The method of preparing 2,2,4,9,9,l5-hexanitro- 4,7,1 LIS-tetraazaheptadecane which comprises condensing 4-nitraza-1-hexylamine and 3-aza-3,5,5-trinitro-1-hexylamine with 2,2-dinitro-1,3-propanediol.

No references cited. 

1. AS A COMPOSITION OF MATTER, DINITRAMINE HAVING THE FORMULA: 